This report describes a method for the deoxyfluorination of alcohols with KF as the fluorine source via in situ generation of highly active CFSOF. Diverse functionalities, including halogen, nitro, ketone, ester, alkene, and alkyne, are well tolerated. Mild conditions, a short reaction time, and a wide substrate scope make this method an excellent choice for the construction of C-F bonds.
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http://dx.doi.org/10.1021/acs.joc.2c00388 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
Organofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2°)-selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane-mediated deoxyfluorination results in high 2°-selectivity in inter- and intra-molecular competition reactions versus primary (1°), tertiary (3°) and even benzylic (Bn) alcohols.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
National and Local Joint Engineering Research Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Deoxyfluorination is one of the most practical methods for introducing fluorine atoms, since hydroxyl groups are commonly found in organic small molecules. Traditional fluorination methods often rely on hazardous fluorinating reagents. Herein, we report the deoxyfluorination of propargyl alcohols using sulfur hexafluoride (SF) as a safe fluorinating agent under photocatalytic conditions.
View Article and Find Full Text PDFJ Org Chem
August 2024
Department of Chemistry and Biochemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1000 Ljubljana, Slovenia.
In the study, we introduce an air-stable NHC-based deoxyfluorination reagent ImCl[HF], offering a promising avenue for deoxyfluorination across various substrates. Reagent efficiently fluorinates benzyl alcohols, carboxylic acids, and P(V) compounds without external fluoride sources. A mechanistic study reveals a two-step process involving benzyl chloride as an intermediate, shedding light on the two-step reaction pathway.
View Article and Find Full Text PDFChemistry
October 2024
Institute of General, Inorganic and Theoretical Chemistry, Universität Innsbruck, 6020, Innsbruck, Austria.
Sulfur based deoxyfluorination reagents are usually derived from the corrosive gas SF. Herein, we report the synthesis and properties of an easily accessible phosphonium salt [(tmg)PF]SF (1) which was obtained from the reaction of sulfur hexafluoride (SF) with tris(tetramethylguanidinyl)phosphine. The performance of this crystalline SF salt as a reagent in deoxyfluorination reactions was investigated together with a second SF salt [(R)PF]SF (2) containing bulky substituents (R=1,3-di-tert-butylimidazolidin-2-ylidenamino).
View Article and Find Full Text PDFJ Am Chem Soc
October 2023
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
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